SABRE hyperpolarization of nicotinamide derivatives and their molecular dynamics properties.

Signal amplification by reversible exchange hyperpolarization explores the chemical structure and kinetic properties of nicotinamide derivatives. N-Benzyl nicotinamide and nicotinic acid hydrazide compounds display relatively fast dissociation rates of approximately 7-8 s-1 and long proton T1 relaxation times of 5-20 s, respectively. Consequently, these substrates exhibit remarkable signal enhancements, reaching approximately 175 and 102 fold, respectively, underscoring the efficacy of the hyperpolarization technique in elucidating the behavior of these compounds.

Dynamic Nuclear Polarization of Selectively 29Si-Enriched Core@shell Silica Nanoparticles.

29Si silica nanoparticles (SiO2 NPs) are promising magnetic resonance imaging (MRI) probes that possess advantageous properties for in vivo applications, including suitable biocompatibility, tailorable properties, and high water dispersibility. Dynamic nuclear polarization (DNP) is used to enhance 29Si MR signals via enhanced nuclear spin alignment; to date, there has been limited success employing DNP for SiO2 NPs due to the lack of endogenous electronic defects that are required for the process. To create opportunities for SiO2-based 29Si MRI probes, we synthesized variously featured SiO2 NPs with selective 29Si isotope enrichment on homogeneous and core@shell structures (shell thickness: 10 nm, core size: 40 nm), and identified the critical factors for optimal DNP signal enhancement as well as the effective hyperpolarization depth when using an exogenous radical. Based on the synthetic design, this critical factor is the proportion of 29Si in the shell layer regardless of core enrichment. Furthermore, the effective depth of hyperpolarization is less than 10 nm between the surface and core, which demonstrates an approximately 40% elongated diffusion length for the shell-enriched NPs compared to the natural abundance NPs. This improved regulation of surface properties facilitates the development of isotopically enriched SiO2 NPs as hyperpolarized contrast agents for in vivo MRI.

Background free in vivo29Si MR imaging with hyperpolarized PEGylated silicon nanoparticles.

This study demonstrated the potential of 50 nm PEGylated Si NPs for high-resolution in vivo29Si MR imaging, emphasizing their biocompatibility and water dispersibility. The acquisition of in vivo Si MR images using the lowest reported dose after subcutaneous and intraperitoneal administration opens new avenues for future 29Si MR studies.

Hyperpolarized 29Si magnetic resonance spectroscopy of selectively radical-embedded silica nanoparticles.

The embedding of radicals at different locations within core@shell silica nanoparticles contributes to enhanced polarization capability and can be self-polarized without adding external radicals. With grafting the radical source homogenously inside of the nanoparticles, a significant 29Si hyperpolarization signal enhancement of 49.4 was obtained.

Raman Scattering Study on the Influence of E-Beam Bombardment on Si Electron Lens.

Microcolumns have a stacked structure composed of an electron emitter, electron lens (source lens), einzel lens, and a deflector manufactured using a micro electro-mechanical system process. The electrons emitted from the tungsten field emitter mostly pass through the aperture holes. However, other electrons fail to pass through because of collisions around the aperture hole. We used Raman scattering measurements and X-ray photoelectron spectroscopy analyses to investigate the influence of electron beam bombardment on a Si electron lens irradiated by acceleration voltages of 0, 20, and 30 keV. We confirmed that the crystallinity was degraded, and carbon-related contamination was detected at the surface and edge of the aperture hole of the Si electron lens after electron bombardment for 24 h. Carbon-related contamination on the surface of the Si electron lens was verified by analyzing the Raman spectra of the carbon-deposited Si substrate using DC sputtering and a carbon rod sample. We report the crystallinity and the origin of the carbon-related contamination of electron Si lenses after electron beam bombardment by non-destructive Raman scattering and XPS analysis methods.

Direct measurement of electrostatic interactions between poly(methyl methacrylate) microspheres with optical laser tweezers.

In this study, we measured the force of electrostatic interactions between poly(methyl methacrylate) (PMMA) particles dispersed in organic solvent mixtures of cyclohexyl bromide (CHB) and n-decane. Optical laser tweezers were employed to directly measure interactive forces between paired PMMA particles in a CHB medium that contained n-decane in various volume ratios. CHB, having a moderate dielectric constant, provided an environment with a high charge storage capacity. The addition of n-decane lowered the effective refractive index of the medium, which increased the optical trapping efficiency. We also fabricated microscope flow cells with a commonly used UV-curable adhesive and quantified the effects of dissolved adhesive compounds through interactive force measurements and nuclear magnetic resonance analysis. In addition, we studied the impact of CHB dissociation into H+ and Br- ions, which could screen electrostatic interactions.

Hyperpolarized Porous Silicon Nanoparticles: Potential Theragnostic Material for 29 Si Magnetic Resonance Imaging.

Porous silicon nanoparticles have recently garnered attention as potentially-promising biomedical platforms for drug delivery and medical diagnostics. Here, we demonstrate porous silicon nanoparticles as contrast agents for 29 Si magnetic resonance imaging. Size-controlled porous silicon nanoparticles were synthesized by magnesiothermic reduction of silica nanoparticles and were surface activated for further functionalization. Particles were hyperpolarized via dynamic nuclear polarization to enhance their 29 Si MR signals; the particles demonstrated long 29 Si spin-lattice relaxation (T1 ) times (∼25 mins), which suggests potential applicability for medical imaging. Furthermore, 29 Si hyperpolarization levels were sufficient to allow 29 Si MRI in phantoms. These results underscore the potential of porous silicon nanoparticles that, when combined with hyperpolarized magnetic resonance imaging, can be a powerful theragnostic deep tissue imaging platform to interrogate various biomolecular processes in vivo.

Cell-Penetrating Peptide-Patchy Deformable Polymeric Nanovehicles with Enhanced Cellular Uptake and Transdermal Delivery.

We herein propose a polymeric nanovehicle system that has the ability to remarkably improve cellular uptake and transdermal delivery. Cell-penetrating peptide-patchy deformable polymeric nanovehicles were fabricated by tailored coassembly of amphiphilic poly(ethylene oxide)- block-poly(ε-caprolactone) (PEO- b-PCL), mannosylerythritol lipid (MEL), and YGRKKRRQRRR-cysteamine (TAT)-linked MEL. Using X-ray diffraction, differential scanning calorimetry, and nuclear magnetic resonance analyses, we revealed that the incorporation of MEL having an asymmetric alkyl chain configuration was responsible for the deformable phase property of the vehicles. We also discovered that the nanovehicles were mutually attracted, exhibiting a gel-like fluid characteristic due to the dipole-dipole interaction between the hydroxyl group of MEL and the methoxy group of PEO- b-PCL. Coassembly of TAT-linked MEL with the deformable nanovehicles significantly enhanced cellular uptake due to macropinocytosis and caveolae-/lipid raft-mediated endocytosis. Furthermore, the in vivo skin penetration test revealed that our TAT-patchy deformable nanovehicles remarkably improved transdermal delivery efficiency.

Copper(I)-Catalyzed Synthesis of 1,4-Disubstituted 1,2,3-Triazoles from Azidoformates and Aryl Terminal Alkynes.

The copper(I)-catalyzed azide-alkyne cycloaddition reaction has been extensively studied and widely applied in organic synthesis. However, the formation of 1,2,3-triazoles with electron-deficient azide has been a challenging problem. In this report, we have demonstrated the formation of regioselective 1,4-disubstituted 1,2,3-triazoles from various types of aryl terminal alkynes and azidoformates, which are electron-deficient azides, using a commercialized [Cu(CH3CN)4]PF6 copper(I) catalyst under mild conditions.

The effects of different hinge positions on posterior tibial slope in medial open-wedge high tibial osteotomy.

PURPOSE: The purpose of this study was to determine the standard hinge position to minimize effects from medial open-wedge high tibial osteotomy (HTO) on the posterior tibial slope. METHODS: Sixteen cadaveric knees underwent medial open-wedge osteotomy using either the standard or the low hinge position. To define the standard hinge position, a line 3 cm inferior to the medial tibial plateau towards the fibular head and located its intersection with a longitudinal line 1 cm medial to the fibular shaft was drawn. Low hinge position was defined as the point 1 cm inferior to the standard position. After tibial osteotomy, computed tomography scans of each knee were taken and three-dimensional models were constructed to characterize hinge position orientation and measure the osteotomy site effects on posterior tibial slope, medial proximal tibial angle, and gap ratio (the ratio of the anterior to posterior gap in the opened wedge). RESULTS: In two low hinge position specimens, the tibial lateral cortex hinge fracture occurred. Osteotomy through the low hinge position resulted in significantly greater posterior tibial slope compared to the standard hinge position (mean ± standard deviation) (11.2 ± 3.0° and 5.6 ± 2.5°, respectively; p < 0.001). Medial proximal tibial angle was also significantly greater for low compared to standard hinge position (95.4 ± 3.5° and 88.0 ± 3.5°, respectively; p < 0.001). Gap ratio was not significantly different between the two groups. CONCLUSION: Hinge position significantly affects the posterior tibial slope and medial proximal tibial angle following medial open-wedge HTO. Accurate hinge position is crucial to prevent complications from changes in posterior tibial slope and medial proximal tibial angle after surgery.

Structurally Stable Attractive Nanoscale Emulsions with Dipole-Dipole Interaction-Driven Interdrop Percolation.

This study introduces an extremely stable attractive nanoscale emulsion fluid, in which the amphiphilic block copolymer, poly(ethylene oxide)-block-poly(ϵ-caprolactone) (PEO-b-PCL), is tightly packed with lecithin, thereby forming a mechanically robust thin-film at the oil-water interface. The molecular association of PEO-b-PCL with lecithin is critical for formation of a tighter and denser molecular assembly at the interface, which is systematically confirmed by T2 relaxation and DSC analyses. Moreover, suspension rheology studies also reflect the interdroplet attractions over a wide volume fraction range of the dispersed oil phase; this results in a percolated network of stable drops that exhibit no signs of coalescence or phase separation. This unique rheological behavior is attributed to the dipolar interaction between the phosphorylcholine groups of lecithin and the methoxy end groups of PEO-b-PCL. Finally, the nanoemulsion system significantly enhances transdermal delivery efficiency due to its favorable attraction to the skin, as well as high diffusivity of the nanoscale emulsion drops.

Direct transfer of multilayer graphene grown on a rough metal surface using PDMS adhesion engineering.

The direct transfer of graphene using polydimethylsiloxane (PDMS) stamping has advantages such as a 'pick-and-place' capability and no chemical residue problems. However, it is not easy to apply direct PDMS stamping to graphene grown via chemical vapor deposition on rough, grainy metal surfaces due to poor contact between the PDMS and graphene. In this study, graphene consisting of a mixture of monolayers and multiple layers grown on a rough Ni surface was directly transferred without the use of an adhesive layer. Liquid PDMS was cured on graphene to effect a conformal contact with the graphene. A fast release of graphene from substrate was achieved by carrying out wet-etching-assisted mechanical peeling. We also carried out a thermal post-curing of PDMS to control the level of adhesion between PDMS and graphene and hence facilitate a damage-free release of the graphene. Characterization of the transferred graphene by micro-Raman spectroscopy, SEM/EDS and optical microscopy showed neither cracks nor contamination from the transfer. This technique allows a fast and simple transfer of graphene, even for multilayer graphene grown on a rough surface.

Tailored synthesis of pH-responsive biodegradable microcapsules incorporating gelatin, alginate, and hyaluronic acid for effective-controlled release.

In response to escalating environmental concerns and the urgent need for sustainable drug delivery systems, this study introduces biodegradable pH-responsive microcapsules synthesized from a blend of gelatin, alginate, and hyaluronic acid. Employing the coacervation process, capsules were created with a spherical shape, multicore structure, and small sizes ranging from 10 to 20 µm, which exhibit outstanding vitamin E encapsulation efficiency. With substantial incorporation of hyaluronic acid, a pH-responsive component, the resulting microcapsules displayed noteworthy swelling behavior, facilitating proficient core ingredient release at pH 5.5 and 7.4. Notably, these capsules can effectively deliver active substances to the dermal layer under specific skin conditions, revealing promising applications in topical medications and cosmetics. Furthermore, the readily biodegradable nature of the designed capsules was demonstrated through Biochemical Oxygen Demand (BOD) testing, with over 80 % of microcapsules being degraded by microorganisms after one week of incubation. This research contributes to the development of responsive microcapsules and aligns with broader environmental initiatives, offering a promising pathway to mitigate the impact of microplastics while advancing various applications.

Detection of living anionic species in polymerization reactions using hyperpolarized NMR.

Intermediates during the anionic polymerization of styrene were observed using hyperpolarized NMR. Dissolution dynamic nuclear polarization (DNP) of monomers provides a sufficient signal-to-noise ratio for detection of (13)C NMR signals in real time as the reaction progresses. Because of its large chemical shift dispersion, (13)C is well-suited to distinguish and characterize the chemical species that arise during the reaction. At the same time, incorporation of hyperpolarized small-molecule monomers is a unique way to generate polymers that exhibit a transient signal enhancement at the active site. This strategy is applicable despite the decay of the hyperpolarization of the polymer due to rapid spin-lattice relaxation. Real-time measurements on polymerization reactions provide both mechanistic and kinetic information without the need for stable isotope labeling of the molecules of interest. These capabilities are orthogonal to currently established methods that separate synthesis and analysis into two steps, making dissolution DNP an attractive method to study polymerization reactions.

Biodegradable Nanofiber/Metal-Organic Framework/Cotton Air Filtration Membranes Enabling Simultaneous Removal of Toxic Gases and Particulate Matter.

The typical filters that protect us from harmful components, such as toxic gases and particulate matter (PM), are made from petroleum-based materials, which need to be replaced with other environmentally friendly materials. Herein, we demonstrate a route to fabricate biodegradable and dual-functional filtration membranes that effectively remove PM and toxic gases. The membrane was integrated using two layers: (i) cellulose-based nanofibers for PM filtration and (ii) metal-organic framework (MOF)-coated cotton fabric for removal of toxic gases. Zeolitic imidazolate framework (ZIF-8) was grown from the surface of the cotton fabric by the treatment of cotton fabric with an organic precursor solution and subsequent immersion in an inorganic precursor solution. Cellulose acetate nanofibers (NFs) were deposited on the MOF-coated cotton fabric via electrospinning. At the optimal thickness of the NF layer, the quality factor of 18.8 × 10-2 Pa-1 was achieved with a filtration efficiency of 93.1%, air permeability of 19.0 cm3/cm2/s, and pressure drop of 14.2 Pa. The membrane exhibits outstanding gas adsorption efficiencies (>99%) for H2S, formaldehyde, and NH3. The resulting membrane was highly biodegradable, with a weight loss of 62.5% after 45 days under standard test conditions. The proposed strategy should provide highly sustainable material platforms for practical multifunctional membranes in personal protective equipment.

Accurate detection of enzymatic degradation processes of gelatin-alginate microcapsule by 1H NMR spectroscopy: Probing biodegradation mechanism and kinetics.

With an increase in the severity of environmental pollution caused by microbeads, the development of biodegradable microcapsules that can be applied in diverse fields has attracted significant attention. The degradation processes are directly related to biodegradable microcapsule creation with high stability and persistence. In this study, biodegradable microcapsules are synthesized via a complex coacervation approach using gelatin and alginate as the capsule main wall materials; additionally, enzyme-induced decomposition mechanisms are proposed by observing spectral changes in proton nuclear magnetic resonance (1H NMR) analyses. Additional analytical techniques confirm the chemical structure, morphology, and size distribution of the synthesized capsules; these uniform spherical microcapsules are 20-30 µm in size and possess a smooth surface. In addition to characterization, the microcapsules were exposed to targeted enzymes to investigate enzymatic effects using short-term and long-term degradation kinetics. Close inspection reveals that determination of the degradation rate constant of the major components in the capsule is feasible, and suggests two types of 4-stage degradation mechanisms that are enzyme-specific. These investigations demonstrate that capsule degradation can be explored in detail using 1H NMR spectroscopy to provide a viable strategy for monitoring degradation properties in the development of new biodegradable polymers.

Nuclear magnetic resonance of hyperpolarized fluorine for characterization of protein-ligand interactions.

Fluorine NMR spectroscopy is widely used for detection of protein-ligand interactions in drug discovery because of the simplicity of fluorine spectra combined with a relatively high likelihood for a drug molecule to include at least one fluorine atom. In general, an important limitation of NMR spectroscopy in drug discovery is its sensitivity, which results in the need for unphysiologically high protein concentrations and large ligand:protein ratios. An enhancement in the (19)F signal of several thousand fold by dynamic nuclear polarization allows for the detection of submicromolar concentrations of fluorinated small molecules. Techniques for exploiting this gain in signal to detect ligands in the strong-, intermediate-, and weak-binding regimes are presented. Similar to conventional NMR analysis, dissociation constants are determined. However, the ability to use a low ligand concentration permits the detection of ligands in slow exchange that are not easily amenable to drug screening by traditional NMR methods. The relative speed and additional information gained may make the hyperpolarization-based approach an interesting alternative for use in drug discovery.

Development of semi-empirical soot emission model for a CI engine.

Soot is one of the main harmful emissions of diesel engines that is mainly generated in the reacting fuel jet of diesel injection. Over 99% of the engine-out soot can be filtered by a diesel particulate filter (DPF). However, when the soot load of the DPF is high, a regeneration process that oxidizes the accumulated soot reduces fuel economy. A real-time soot estimation model can contribute to real-time feedback soot control under transient conditions to minimize the engine-out soot emission and frequency of DPF regeneration. A zero-dimensional engine-out soot estimation model for a diesel engine is developed in this study. The semi-empirical soot model considers both the formation and oxidation of soot. In the model, soot formation was correlated with the cross-sectional average equivalence ratio at the lift-off length of the fuel spray. The equivalence ratio at the lift-off length is an indicator of how much air and vaporized fuel are mixed as the fuel reaches the reaction zone. The mass of the injected fuel and combustion duration were also correlated with soot formation. The Nagle and Strickland-Constable mechanism, which calculates the soot oxidation rate was correlated with the soot oxidation in this study. The results of the soot estimation showed an R2 of 0.901 and root mean square error of 10.8 mg/m3 for steady-state experimental cases. The engine-out soot model was also combined with the in-cylinder pressure model proposed by the authors, and validated through the transient Worldwide Harmonized Light Vehicles Test Cycle (WLTC) mode. The estimates agreed with the measured soot, with an accumulated soot error of approximately 6% during the WLTC, even without using an in-cylinder pressure sensor. The soot model developed in this study can help minimize tailpipe-out soot emissions and improve fuel economy by influencing the real-time feedback control during transient and frequent DPF regeneration.

Polyphenol-modified nanovesicles for synergistically enhanced in vitro tumor cell targeting and apoptosis.

Tannic acid (TA) not only prevents drug carriers from sticking to the glycocalyx layer of vascular endothelial cells but also has anti-cancer properties, thereby improving drug delivery efficiency in cancer treatment. This study proposes a TANNylated nanovesicle-based cancer treatment approach by utilizing the aforementioned advantages of TA. We fabricated cancer cell-targeting BC71 peptide-conjugated TANNylated nanovesicles (TANVBC71) by covalently bonding the TA derivative and BC71 (cyclo[ßA-kRK(3-maleimidopropionyl)-D-(D-2-naphthyl)]) with thiol-modified phospholipids through the thiol-maleimide reaction. We demonstrated that TANVBC71 was absorbed faster in high amounts by cancer cells than nanovesicles owing to its high affinity for the epidermal growth factor receptor and extracellular matrix components that are driven by van der Waals attraction as well as hydrogen bonding and hydrophobic interactions in a complex manner. These complex attractions of TANVBC71 for cancer cells led to the effective induction of cancer cell apoptosis. The findings obtained in this study highlight that the TANVBC71 system has the potential for intelligent high-efficacy cancer cell drug delivery.

Severe Scalp Psoriasis Microbiome Has Increased Biodiversity and Relative Abundance of Pseudomonas Compared to Mild Scalp Psoriasis.

Psoriasis is a chronic inflammatory skin disease associated with various factors. Recently, alterations in the gut and skin microbiomes have been shown to interact with host immunity, affect skin barrier function, as well as development and progression of psoriasis. We aimed to analyze the microbiota of the scalp of patients with psoriasis and determine the characteristics of the microbiome according to disease severity. We investigated the scalp microbiome of 39 patients with psoriasis scalp lesions and a total of 47 samples were analyzed. The patients were divided into mild, moderate, and severe groups according to the European recommendations for scalp psoriasis. For bacterial identification, we utilized the SILVA database targeting the V3 region of the 16 S rRNA gene. The mean Shannon index escalated along with disease severity, and the diversity of the scalp microbiome tended to increase with disease severity (R = 0.37, p < 0.01). The relative abundance of Pseudomonas was increased in severe scalp psoriasis (0.49 ± 0.22) compared to the mild group (0.07 ± 0.03, p = 0.029), and Diaphorobacter was enriched in the mild group (0.76 ± 0.16%) compared to the severe group (0.44 ± 0.22, p < 0.001). We identified that increased diversity of the scalp microbiome and the relative abundance of Pseudomonas are associated with the severity of scalp psoriasis.